Dye mixtures of fiber-reactive azodyes and the use thereof

ABSTRACT

Reactive dye mixtures containing one or more dyes of the general formula (I)  
                 
 
     and one or more dyes of the general formula (II)  
                 
 
     or one more dyes of the general formula (III)  
                 
 
     where  
     D −1  to D 4 , R 31  to R 33 , Z 31 , a, b, c, f, r, t and M are each as defined in claim 1, are prepared and used for dyeing hydroxyl- and carboxamido-containing material.

[0001] This invention relates to the technical field of fiber-reactiveazo dyes.

[0002] Mixed fiber-reactive azo dyes and their use for dyeing hydroxyl-and carboxamido-containing material in black shades are known forexample from the documents U.S. Pat. No. 5,445,654, U.S. Pat. No.5,611,821, KR 94-2560, Sho 58-160362 and EP-A-0 870 807. However, theyhave certain application defects, such as for example an overly largedependence of the color yield on varying dyeing parameters in the dyeingprocess or an insufficient or unlevel color build-up on cotton (goodcolor build-up results from the ability of a dye to provide aproportionally stronger dyeing when used in higher concentrations in thedyebath), or an excessive salt dependence of the dyeings. Consequencesof these defects can be poor reproducibilities for the dyeings that areobtainable. The documents WO 98/42784, WO 98/42785, WO 93/18224 and U.S.Pat. No. 5,330,539 disclose dyes and dye mixtures which can be dyed inthe presence of small amounts of salt, but which provide only very weakdyeings in the absence of salt.

[0003] Since it is commercially as well as environmentally necessary toreduce the salt content of dyeing effluent, there is a need for reactivedyes which provide dyeings of high color strength in the presence ofsmall amounts of salt or even in the absence of electrolyte salts.

[0004] The present invention, then, provides dye mixtures which providedyeings of high color strength in the presence of only very low levelsor even in the absence of electrolyte salts.

[0005] The invention accordingly provides dye mixtures comprising one ormore, such as two or three, preferably 1 or 2, dyes of the hereinbelowindicated and defined general formula (I)

[0006] and one or more, such as two or three, preferably 1 or 2, dyes ofthe hereinbelow indicated and defined general formula (II)

[0007] or one or more, such as two or three, preferably 1 or 2, dyes ofthe hereinbelow indicated and defined general formula (III)

[0008] where:

[0009] D¹ and D² are each a group of the general formula (1)

[0010] where

[0011] R¹ is hydrogen, (C₁-C₄)-alkyl, aryl or a substituted arylradical;

[0012] R² and R³ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

[0013] A is a phenylene group of the general formula (2)

[0014]  where

[0015] R⁴ and R⁵ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or

[0016] a naphthylene group of the general formula (3)

[0017]  where

[0018] R⁶ and R⁷ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or

[0019] a polymethylene group of the general formula (4)

—(CR⁸R⁹)_(k)—  (4)

[0020]  where

[0021] k is an integer greater than 1 and

[0022] R⁸ and R⁹ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and

[0023] X¹ is hydrogen or a group of the formula —SO₂-Z; or

[0024] are each a phenyl group of the general formula (5)

[0025] where

[0026] R¹⁰ and R¹¹ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

[0027] X² has one of the meanings of X¹;

[0028] or are each a naphthyl group of the general formula (6)

[0029] where

[0030] R¹² and R¹³ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

[0031] X³ has one of the meanings of X₁;

[0032] Z is —CH═CH₂, —CH₂CH₂Z¹ or hydroxyl,

[0033] where

[0034] Z¹ is hydroxyl or an alkali-eliminable group; and

[0035] M is hydrogen, an alkali metal or one equivalent of an alkalineearth metal;

[0036] D³ and D⁴ independently have one of the meanings of D¹ or D² orare each a group of the general formula (7) or (8)

[0037]  where

[0038] R²² and R²³ independently have one of the meanings of R² and R³;

[0039] R²¹ is hydrogen, (C₁-C₄)-alkyl, unsubstituted or (C₁-C₄)-alkyl-,(C₁-C₄)-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; and

[0040] Z²¹ is a group of the general formula (9) or (10) or (11)

[0041]  where

[0042] V is fluorine or chlorine;

[0043] U¹ and U² are independently fluorine, chlorine or hydrogen; and

[0044] Q¹ and Q² are independently chlorine, fluorine, cyanamido,hydroxyl, (C₁-C₆)-alkoxy, phenoxy, sulfophenoxy, mercapto,(C₁-C₆)-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or agroup of the general formula (12) or (13)

[0045]  where

[0046] R²′ is hydrogen or (C₁-C₆)-alkyl, sulfo-(C₁-C₆)-alkyl, or phenylwhich is unsubstituted or substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,sulfo, halogen, carboxyl, acetamido or ureido;

[0047] R³′ and R⁴′ independently have one of the meanings of R²′ or areeach a group of the general formula (8), or combine to form a cyclicring system of the formula —(CH₂)_(j)—, where j is 4 or 5, oralternatively —(CH₂)₂-E-(CH₂)₂—, where E is oxygen, sulfur, sulfo,—NR⁵′—, where R⁵′═(C₁-C₆)-alkyl;

[0048] W is phenylene which is unsubstituted or substituted by 1 or 2substituents, such as (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, carboxyl, sulfo,chlorine, bromine, or is (C₁-C₄)-alkylene-arylene or (C₂-C₆)-alkylene,which can be interrupted by oxygen, sulfur, sulfo, amino, carbonyl,carboxamido, or is phenylene-CONH-phenylene, which is unsubstituted orsubstituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl,amido, ureido or halogen, or is naphthylene, which is unsubstituted orsubstituted by one or two sulfo groups; and

[0049] Z is as defined above;

[0050] R²⁴, R²⁵ and R²⁶ are each (C₁-C₄)-alkyl or (C₁-C₄)-hydroxyalkyl;

[0051] B⁻ is the equivalent of an anion, such as hydrogensulfate,sulfate, fluoride, chloride, bromide, dihydrogenphosphate,hydrogenphosphate, phosphate, hydroxide or acetate;

[0052] R³¹ R³², R³³ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, carboxyl, halogen, (C₁-C₄)-alkylcarbonylamino,benzoylamino, ureido;

[0053] R³² is hydrogen, (C₁-C₄)-alkyl;

[0054] Z³¹ has one of the meanings of Z²¹;

[0055] a, b, c are independently 0 or 1;

[0056] f, r are independently 0, 1 or 2; and

[0057] t is 1, 2 or 3.

[0058] In the general formula (I) at least one of D¹ and D² is a groupof the general formula (1);

[0059] when A is a group of the general formula (4), R¹ is aryl orsubstituted aryl; and the reactive dye of the general formula (I)contains at least one —SO₂-Z group.

[0060] The individual symbols in the general formulae above and belowcan have identical or different meanings under their definition,irrespective of whether the symbols bear the same or a differentdesignation.

[0061] (C₁-C₄)-Alkyl R may be straight-chain or branched and is inparticular methyl, ethyl, n-propyl, isopropyol, n-butyl, isobutyl,sec-butyl or tert-butyl. Methyl and ethyl are preferred. The same logicapplies to (C₁-C₄)-alkoxy groups.

[0062] Aryl R is in particular phenyl. Substituted aryl R¹ is inparticular phenyl substituted by one, two or three independent groupsselected from the group consisting of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,hydroxyl, sulfo, carboxyl, amido and halogen. Halogen R is in particularfluorine, chlorine or bromine, and chlorine and bromine are preferred.

[0063] Alkali-eliminable Z¹ in the β-position of the ethyl group of Zinclude for example halogen atoms, such as chlorine and bromine, estergroups of organic carboxylic and sulfonic acids, as of alkylcarboxylicacids, substituted or unsubstituted benzenecarboxylic acids andsubstituted or unsubstituted benzenesulfonic acids, such as alkanoyloxyof 2 to 5 carbon atoms, especially acetyloxy, benzoyloxy,sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy, also acidicester groups of inorganic acids, as of phosphoric acid, sulfuric acidand thiosulfuric acid (phosphato, sulfato and thiosulfato groups),similarly dialkylamino groups having alkyl groups of 1 to 4 carbon atomsin each case, such as dimethylamino and diethylamino.

[0064] Z is preferably vinyl, β-chloroethyl and particularly preferablyβ-sulfatoethyl.

[0065] The groups “sulfo”, “carboxyl”, “thiosulfato”, “phosphate” and“sulfato” include not only their acid form but also their salt form.Accordingly, sulfo groups are groups conforming to the general formula—SO₃M, thiosulfato groups are groups conforming to the general formula—S—SO₃M, carboxyl groups are groups conforming to the general formula—COOM, phosphato groups are groups conforming to the general formula—OPO₃M₂ and sulfato groups are groups conforming to the general formula—OSO₃M, in each of which M is as defined above.

[0066] The dyes of the general formula (I) to (III) may possessdifferent fiber-reactive groups —SO₂Z within the meaning of Z. Moreparticularly, the fiber-reactive groups —SO₂Z may be on the one handvinylsulfonyl groups and on the other —CH₂CH₂Z¹ groups, preferablyβ-sulfatoethylsulfonyl groups. If the dyes of the general formula (I) to(III) contain vinyl-sulfonyl groups in some instances, then the fractionof the respective dye with the vinylsulfonyl group is up to about 30 mol%, based on the respective amount of total dye.

[0067] Alkali M is in particular lithium, sodium or potassium. M ispreferably hydrogen or sodium.

[0068] k is preferably 2 or 3.

[0069] R¹ to R¹³ are each preferably hydrogen and R⁶, R⁷, R¹² and R¹³are each preferably sulfo as well.

[0070] When A is phenylene and X¹ is —SO₂Z, the SO₂Z group is preferablydisposed meta or para relative to the nitrogen atom. In the group of thegeneral formula (1), the carboxamide group is preferably disposed paraor meta relative to the diazo group. When A is naphthylene, the bondleading to the nitrogen atom is preferably attached to the naphthalenenucleus in the β-position. When D¹ or D² is a group of the generalformula (6), then the bond which leads to the diazo group is preferablyattached to the naphthalene nucleus in the β-position.

[0071] When D¹ or D² is a group of the general formula (5) and X² is—SO₂Z, then the SO₂Z group is preferably disposed meta or para relativeto the diazo group.

[0072] Examples of substituents A are in particular 1,2-phenylene,1,3-phenylene, 1,4-phenylene, 2-chloro-1,4-phenylene,2-chloro-1,5-phenylene, 2-bromo-1,4-phenylene, 2-sulfo-1,4-phenylene,2-sulfo-1,5-phenylene, 2-methoxy-1,5-phenylene, 2-ethoxy-1,5-phenylene,2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene,2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene,1-sulfo-2,6-naphthylene, 6-sulfo-2,8-naphthylene or 1,2-ethylene and1,3-propylene.

[0073] A is particularly preferably 1,3-phenylene, 1,4-phenylene,2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene,2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene or1,2-ethylene and 1,3-propylene, and in the case of the twolast-mentioned alkylene groups R¹ is preferably phenyl or 2-sulfophenyl.

[0074] Examples of groups D¹ and D² of the general formulae (5) and (6)are 2-(β-sulfato-ethylsulfonyl)-phenyl,3-(β-sulfatoethylsulfonyl)-phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl,2-carboxy-5-(β-sulfatoethylsulfonyl)-phenyl,2-chloro-4-(β-sulfatoethyl-sulfonyl)-phenyl,2-chloro-5-(β-sulfatoethylsulfonyl)-phenyl,2-bromo-4-(β-sulfato-ethylsulfonyl)-phenyl,2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl,2-sulfo-5-(β-sulfato-ethylsulfonyl)-phenyl,2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl,2-ethoxy-5-(β-sulfatoethylsulfonyl)-phenyl,2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl,2-methyl-4-(β-sulfatoethyl-sulfonyl)-phenyl, 2- or 3- or4-(β-thiosulfatoethylsulfonyl)-phenyl,2-methoxy-5-(β-thiosulfatoethylsulfonyl)-phenyl,2-sulfo-4-(β-phosphatoethylsulfonyl)-phenyl, 2-or 3- or4-vinylsulfonyl-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl,2-chloro-4-(β-chloro-ethylsulfonyl)-phenyl,2-chloro-5-(β-chloroethylsulfonyl)-phenyl, 3- or4-(β-acetoxyethylsulfonyl)-phenyl, 6- or8-(β-sulfatoethylsulfonyl)-naphth-2-yl,6-(β-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl and8-(β-sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl, preferably3-(β-sulfatoethylsulfonyl)-phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl,2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-(β-sulfato-ethylsulfonyl)-phenyl,2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl and 3- or4-vinylsulfonyl-phenyl.

[0075] In the general formula (II), D³ and D⁴ are each preferably3-(β-sulfatoethylsulfonyl)-phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl,2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl,2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl, 3- or4-vinylsulfonyl-phenyl,1-sulfo-4-(2,4-difluoro-pyrimidin-6-yl)-amino-2-phenyl or1-sulfo-4-(4,6-difluoro-pyrimidin-2-yl)-amino-2-phenyl or a group of thegeneral formula (1), where A, R¹ to R³ and X¹ each have the preferredmeanings described above.

[0076] In the general formula (7), R²¹ to R²³ are each preferablyhydrogen and R²² and R²³ are preferably sulfo as well.

[0077] In the general formula (8), R²⁴ to R²⁶ are each preferably methylor ethyl.

[0078] B⁻ is preferably sulfate or chloride.

[0079] In the general formulae (12) and (13), R²′ to R⁴′ are eachpreferably hydrogen or methyl, R²′ is preferably phenyl as well and R³′and R⁴′ are each preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl, 3- or4-trimethyl-ammoniophenyl sulfate, 3- or 4-trimethylammoniophenylchloride, or R³′ and R⁴′ combine to form a cyclic ring system whichpreferably conforms to the formula —(CH₂)₂—O—(CH₂)₂—.

[0080] W is preferably 1,3-phenylene, 1,4-phenylene,2-sulfo-1,4-phenylene, 2-mrethoxy-1,5-phenylene,2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene,1,2-ethylene, 1,3-propylene.

[0081] Q¹ and Q² are independently preferably fluorine, chlorine,carboxypyridino, carbamoylpyridino or a group of the general formula(12) or (13) where R²′ to R⁴′ each have the preferred meanings and W andZ each have the abovementioned meanings.

[0082] Examples of the groups Z²¹ and Z are2,4-dichloro-1,3,5-triazin-6-yl, 2-chloro-4-hydroxy-1,3,5-triazin-6-yl,2-chloro-4-methoxy-1,3,5-triazin-6-yl,2-chloro-4-phenoxy-1,3,5-triazin-6-yl,2-chloro-4-(4-sulfophenoxy)-1,3,5-triazin-6-yl,2-chloro-4-methylmercapto-1,3,5-triazin-6-yl,2-chloro-4-morpholino-1,3,5-triazin-6-yl,2-chloro-4-phenylamino-1,3,5-triazin-6-yl,2-chloro-4-methylphenylamino-1,3,5-triazin-6-yl,2-chloro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2,5-disulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-trimethylammonio-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-sulfoethylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-carboxypyridino)-1,3,5-triazin-6-yl,2-chloro-4-(4-carboxypyridino)-1,3,5-triazin-6-yl,2-chloro-4-(3-carbamoylpyridino)-1,3,5-triazin-6-yl,2-chloro-4-(4-carbamoyl-pyridino)-1,3,5-triazin-6-yl,2-chloro-4-(2-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-ethyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-carboxy-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-chloro-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-chloro-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-bromo-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-sulfo-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-sulfo-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-methoxy-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2,5-dimethoxy-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-methoxy-5-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(2-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-ethyl-4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(6-(2-sulfatoethylsulfonyl)-naphth-2-ylamino)-1,3,5-triazin-6-yl,2-chloro-4-(8-(2-sulfatoethylsulfonyl)-naphth-2-ylamino)-1,3,5-triazin-6-yl,2-chloro-4-(8-(2-sulfatoethylsulfonyl)-6-sulfo-naphth-2-ylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phbnylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-(vinylsulfonyl)-ethylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(N-methyl-2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(N-phenyl-2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenyl-amino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(3-(2-sulfatoethylsulfonyl)-phenyl-carbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(4-(2-sulfatoethyl-sulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-propylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-chloro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-hydroxy-1,3,5-triazin-6-yl,2-fluoro-4-methoxy-1,3,5-triazin-6-yl,2-fluoro-4-phenoxy-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenoxy)-1,3,5-triazin-6-yl,2-fluoro-4-morpholino-1,3,5-triazin-6-yl,2-fluoro-4-phenylamino-1,3,5-triazin-6-yl,2-fluoro-4-methylphenylamino-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2,5-disulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfato-ethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-ethyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-carboxy-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-chloro-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-chloro-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-bromo-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfo-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfo-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-methoxy-5-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2,5-dimethoxy-4-(2-sulfatoethyl-sulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-methoxy-5-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-ethyl-4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(1,3,5-triazin-6-yl,2-fluoro-4-(4-(N-methyl-2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(N-phenyl-2-(2-sulfatoethylsulfonyl)-ethyicarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(3-(2-sulfato-ethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-propylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2,4-di(4-(2-sulfato-ethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2,4-di(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-(3-(2-sulfatoethylsulfonyl)-phenylamino)-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-(N-ethyl-4-(2-sulfato-ethylsulfonyl)-phenylamino)-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-(N-ethyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-4-(3-(2-sulfatoethyl-sulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-(N-ethyl-3-(2-sulfatoethylsulfonyl)-phenylamino)-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-(N-ethyl-3-(2-sulfatoethylsulfonyl)-phenylamino)-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2,4-di(N-ethyl-4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2,4-di(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2,4-di(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-(3-carboxy-pyridino)-4-morpholino-1,3,5-triazin-6-yl,2-(4-carboxypyridino)-4-(3-sulfophenyl-amino)-1,3,5-triazin-6-yl,2-(3-carbamoylpyridino)-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl,2-(4-carbamoylpyridino)-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl,5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl, 4,5-difluoro-pyrimidin-6-yl,5-chloro-4-fluoro-pyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-6-yl,4,5-dichloro-pyrimidin-6-yl, 2,4-dichloro-pyrimidin-6-yl,4-fluoro-pyrimidin-6-yl, 4-chloro-pyrimidin-6-yl,2,3-dichloroquinoxaline-6-carbonyl.

[0083] Preferably Z²¹ is 2,4-dichloro-1,3,5-triazin-6-yl,2-chloro-4-morpholino-1,3,5-triazin-6-yl,2-chloro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-carboxypyridino)-1,3,5-triazin-6-yl,2-chloro-4-(4-carboxypyridino)-1,3,5-triazin-6-yl,2-chloro-4-(3-carbamoyl-pyridino)-1,3,5-triazin-6-yl,2-chloro-4-(4-carbamoylpyridino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-chloro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-morpholino-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfophenyl-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-trimethylammonio-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl,5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl.

[0084] Particularly preferably Z²¹ is 2,4-dichloro-1,3,5-triazin-6-yl,2-chloro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(2-sulfato-ethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2,4-difluoro-pyrimidin-6-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl.

[0085] In the general formula (II), the bond leading to the diazo grouppreferably attaches to the naphthalene nucleus in the β-position when D³or D⁴ represent a group of the general formula (6).

[0086] When D³ or D⁴ represent a group of the general formula (5) and X²is —SO₂Z, the SO₂Z group is preferably meta or para to the diazo group.When D³ or D⁴ represent a group of the general formula (8), thequaternary ammonium group is preferably meta or para to the diazo group.

[0087] In the general formula (III), R³¹ to R³³ are each preferablyhydrogen or methyl, R³¹ is also preferably ureido as well, R³² isacetylamino or ureido and R³³ is methoxy.

[0088] Z³¹ is preferably 2,4-dichloro-1,3,5-triazin-6-yl,2-chloro-4-(3-carboxypyridino)-1,3,5-triazin-6-yl,2-chloro-4-(4-carboxypyridino)-1,3,5-triazin-6-yl,2-chloro-4-(3-carbamoylpyridino)-1,3,5-triazin-6-yl,2-chloro-4-(4-carbamoylpyridino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-chloro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-morpholino-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(2-sulfato-ethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl,5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl,2,3-dichloroquinoxaline-6-carbonyl.

[0089] Most preferably, Z³¹ is 2,4-dichloro-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-chloro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-morpholino-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfophenyl-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-trimethylammonio-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl,5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl,2,3-dichloroquinoxaline-6-carbonyl.

[0090] Preferred mixtures contain one or more dyes of the generalformula (Ia)

[0091] one or more dyes of the general formula (IIa)

[0092] or one or more dyes of the general formula (IIIa)

[0093] In the general formulae (Ia) to (IIa), M, A, R¹, Z, R³¹, R³³, Z³¹and t are each as defined above.

[0094] In the general formula (Ia), it is particularly preferable for Ato be phenylene and Z to be vinyl or β-sulfatoethyl and it is mostpreferable in the formula (Ia) for A to be phenylene, R¹ to be hydrogenand Z to be vinyl or β-sulfatoethyl.

[0095] In the general formula (IIa), R¹⁰³, R¹¹³, R¹⁰⁴ and R¹¹⁴ areindependently hydrogen, methyl, methoxy, sulfo, carboxyl or halogen, andmore preferably R¹⁰³, R¹¹³, R¹⁰⁴ and R¹¹⁴ are each hydrogen, methyl,methoxy or sulfo.

[0096] The dye mixtures according to the invention contain bisazo dyesof the general formula (I) in an amount of 30 to 95% by weight andpreferably 50 to 90% by weight and bisazo dyes of the general formula(II) or (III) in an amount of 5 to 70% by weight and preferably 10 to50% by weight.

[0097] Optionally, the dye mixtures according to the invention may alsocontain one or more monoazo dyes of the general formulae (14) or (15) inan amount of up to 10% by weight,

[0098] where M and D² are each as defined above. It is particularlypreferable for D² to be 4-(2-sulfatoethylsulfonyl)-phenyl or4-vinylsulfonyl-phenyl.

[0099] The dye mixtures according to the invention can be present as apreparation in solid or liquid (dissolved) form. In solid form, theycontain, to the extent necessary, the electrolyte salts customary in thecase of water-soluble and especially fiber-reactive dyes, such as sodiumchloride, potassium chloride and sodium sulfate, and may further containthe auxiliaries customary in commercial dyes, such as buffer substancescapable of setting a pH in aqueous solution between 3 and 7, for examplesodium acetate, sodium citrate, sodium borate, sodium bicarbonate,sodium dihydrogenphosphate and disodium hydrogenphosphate, also dyeingauxiliaries, dustproofing agents and small amounts of siccatives; whenthey are present in a liquid, aqueous solution (including a content ofthickeners of the type customary in print pastes), they may also containsubstances which ensure a long life for these preparations, for examplemold preventatives.

[0100] In solid form, the dye mixtures according to the invention aregenerally present as powders or granules which contain electrolyte saltand which will hereinbelow generally be referred to as a preparationwith or without one or more of the abovementioned auxiliaries. In thepreparations, the dye mixture is present at 20 to 90% by weight, basedon the preparation containing it. The buffer substances are generallypresent in a total amount of up to 10% by weight, based on thepreparation.

[0101] When the dye mixtures according to the invention are present inan aqueous solution, the total dye content of these aqueous solutions isup to about 50% by weight, for example between 5 and 50%, theelectrolyte salt content of these aqueous solutions preferably beingbelow 10% by weight, based on the aqueous solution; the aqueoussolutions (liquid preparations) can contain the aforementioned buffersubstances in an amount which is generally up to 5% by weight andpreferably up to 2% by weight.

[0102] Dyes of the general formula (I) are known from EP-A-1 046 677,dyes of the general formula (II) are known from EP-A-0 785 237 and dyesof the general formula (III) are known from U.S. Pat. No. 3,950,128, A,EP-A-0 042 108, EP-A-0 202 570, DE-A-0303081, EP-A-0 042 108 A, DE-A-3517 366, GB 1 102 204, EP-A-0 319 845 A, EP-A-0575909, DE-A-2 733 109,DE-A-2 804 248, EP-A-0601361. Dyes of the general formulae (14) and (15)are obtainable via standard synthetic methods or are in some instancesformed during the synthesis of dyes of the general formula (I). They arecustomarily used as shading components.

[0103] The dye mixtures according to the invention are preparable in aconventional manner, as by mechanically mixing the individual dyes,whether in the form of dye powders or granules or their as-synthesizedsolutions or in the form of aqueous solutions of the individual dyesgenerally, which may additionally contain customary auxiliaries, or byconventional diazotization and coupling of suitable mixtures of diazoand coupling components in the desired amount ratios.

[0104] For example, when the groups D¹ and D⁴ in the general formula (I)and (II) have the same meanings, an amine of the general formula (16)

D¹—NH₂  (16)

[0105] where D¹ is as defined, can be diazotized in a conventionalmanner and the resulting diazonium compound then reacted with an aqueoussolution or suspension of a mixture having a defined ratio of a monoazodye conforming to the general formula (14) and of a monoazo dyeconforming to the general formula (17)

[0106] where D², D³ and M are each as defined in claim 1, at a pHbetween 4 and 8.

[0107] Alternatively, the dye mixture according to the invention in thecase where the groups D² and D³ and also D¹ and D⁴ in the generalformulae (I) and (II) have the same meaning (D²=D³ and D¹=D⁴) can beprepared by diazotizing an amine of the general formula (18) where D² isas defined above in a conventional manner and coupling the resultingdiazonium compound of a mixture of the coupling components at a pH ofbelow 2 in a first step and subsequently diazotizing an amine of thegeneral formula (16) and coupling the resulting diazonium compound withthe mixture of the monoazo dyes of the general formulae (14) and (17),at a pH of between 4 and 8, that is obtained in the first step.

[0108] The dye mixture according to the invention is isolated in aconventional manner by salting out for example with sodium chloride orpotassium chloride or by spray drying.

[0109] Dye mixtures which as well as β-chloroethylsulfonyl orβ-thiosulfatoethylsulfonyl or β-sulfatoethylsulfonyl groups also containvinylsulfonyl groups as reactive radicals can be synthesized not onlystarting from appropriately substituted vinylsulfonylanilines ornaphthylamines but also by reaction of a dye mixture where Z isβ-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl with an amount ofalkali required for the desired fraction and converting theβ-substituted ethylsulfonyl groups mentioned into vinylsulfonyl groups.This conversion is effected in a manner familiar to one skilled in theart.

[0110] The dye mixtures according to the invention have usefulapplication properties. They are used for dyeing or printing hydroxyl-and/or carboxamido-containing materials, for example in the form ofsheetlike structures, such as paper and leather or of films, for examplecomposed of polyamide, or in bulk, as for example polyamide andpolyurethane, but especially for dyeing and printing these materials infiber form. Similarly, the as-synthesized solutions of the dye mixturesaccording to the invention can be used directly as a liquid preparationfor dyeing, if appropriate after addition of a buffer substance and ifappropriate after concentration or dilution.

[0111] The present invention thus also provides for the use of the dyemixtures according to the invention for dyeing or printing thesematerials, or rather processes for dyeing or printing these materials ina conventional manner, by using a dye mixture according to the inventionor its individual components (dyes) individually together as a colorant.The materials are preferably employed in the form of fiber materials,especially in the form of textile fibers, such as woven fabrics oryarns, as in the form of hanks or wound packages.

[0112] Hydroxyl-containing materials are those of natural or syntheticorigin, for example cellulose fiber materials or their regeneratedproducts and polyvinyl alcohols. Cellulose fiber materials arepreferably cotton, but also other vegetable fibers, such as linen, hemp,jute and ramie fibers; regenerated cellulose fibers are for examplestaple viscose and filament viscose and also chemically modifiedcellulose fibers, such as aminated cellulose fibers or fibers asdescribed for example in WO 96/37641 and WO 96/37642 and also in EP-A-0538 785 and EP-A-0 692 559.

[0113] Carboxamido-containing materials are for example synthetic andnatural polyamides and polyurethanes, especially in the form of fibers,for example wool and other animal hairs, silk, leather, nylon-6,6,nylon-6, nylon-11 and nylon-4.

[0114] The dye mixtures according to the invention can be applied to andfixed on the substrates mentioned, especially the fiber materialsmentioned, by the application techniques known for water-soluble dyesand especially for fiber-reactive dyes. For instance, on cellulosefibers they produce by the exhaust method from a long liquor and alsofrom a short liquor, for example in a liquor to goods ratio of 5:1 to100:1, preferably 6:1 to 30:1, using various acid-binding agents andoptionally neutral salts as far as necessary, such as sodium chloride orsodium sulfate, dyeings having very good color yields. Application ispreferably from an aqueous bath at temperatures between 40 and 105° C.,optionally at a temperature of up to 130° C. under superatmosphericpressure, but preferably at 30 to 95° C., especially 45 to 65° C., inthe presence or absence of customary dyeing auxiliaries. One possibleprocedure here is to introduce the material into the bath and togradually heat the bath to the desired dyeing temperature and completethe dyeing process at that temperature. The neutral salts whichaccelerate the exhaustion of the dyes may also if desired only be addedto the bath after the actual dyeing temperature has been reached.

[0115] Padding processes likewise provide excellent color yields and avery good color build-up on cellulose fibers, the dyes being fixable ina conventional manner by batching at room temperature or elevatedtemperature, for example at up to 60° C., or in a continuous manner, forexample by means of a pad-dry-pad steam process, by steaming or usingdry heat.

[0116] Similarly, the customary printing processes for cellulose fibers,which can be carried out in one step, for example by printing with aprint paste containing sodium bicarbonate or some other acid-bindingagent and by subsequent steaming at 100 to 103° C., or in two steps, forexample by printing with a neutral to weak acidic print color and thenfixing either by passing the printed material through hotelectrolyte-containing alkaline bath or by overpadding with an alkalineelectrolyte-containing padding liquor and subsequent batching of thealkali-overpadded material or subsequent steaming or subsequent dry heattreatment of the alkali-overpadded material, produce strong prints withwell-defined contours and a clear white ground. The outcome of theprints is little affected, if at all, by variations in the fixingconditions.

[0117] When fixing by means of dry heat in accordance with the customarythermofix processes, hot air at 120 to 200° C. is used. In addition tothe customary steam at 101 to 103° C., it is also possible to usesuperheated steam and high-pressure steam at temperatures of up to 160°C.

[0118] The acid-binding agents which effect the fixation of the dyemixtures according to the invention on the cellulose fibers are forexample water-soluble basic salts of alkali metals and likewise alkalineearth metals of inorganic or organic acids or compounds which liberatealkali in the heat, and also alkali metal silicates. Especially suitableare the alkali metal hydroxides and alkali metal salts of weak to mediuminorganic or organic acids, the preferred alkali metal compounds beingthe sodium and potassium compounds. Such acid-binding agents are forexample sodium hydroxide, potassium hydroxide, sodium carbonate, sodiumbicarbonate, potassium carbonate, sodium formate, sodiumdihydrogenphosphate, disodium hydrogenphosphate, sodiumtrichloroacetate, trisodium phosphate waterglass or mixtures thereof,for example mixtures of aqueous sodium hydroxide solution andwaterglass.

[0119] The dye mixtures according to the invention are notable foroutstanding color strength when applied to the cellulose fiber materialsby dyeing or printing in the presence of no or very small amounts ofalkali or alkaline earth metal compounds. For instance, no electrolytesalt is required for a shallow depth of shade, not more than 5 g/l ofelectrolyte salt is required for a medium depth of shade and not morethan 10 g/l of electrolyte salt is required for deep shades.

[0120] According to the invention, a shallow depth of shade refers tothe use of 2% by weight of dye based on the substrate to be dyed, amedium depth of shade refers to the use of 2 to 4% by weight based onthe substrate to be dyed and a deep shade refers to the use of 4 to 10%by weight of dye based on the substrate to be dyed.

[0121] The dyeing and prints obtainable with the dye mixtures accordingto the invention possess bright shades; more particularly, the dyeingsand prints on cellulose fiber materials possess good lightfastness andespecially good wetfastnesses, such as fastness to washing, milling,water, seawater, crossdyeing and acidic and alkaline perspiration, alsogood fastness to pleating, hotpressing and rubbing. Furthermore, thecellulose dyeings obtained following the customary aftertreatment ofrinsing to remove unfixed dye portions exhibit excellent wetfastnesses,in particular since unfixed dye portions are easily washed off becauseof their good solubility in cold water.

[0122] Furthermore, the dye mixtures according to the invention can alsobe used for the fiber-reactive dyeing of wool. Moreover, wool which hasbeen given a nonfelting or low-felting finish (cf. for example H. Rath,Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972), pages295-299, especially finished by the Hercosett process (page 298); J.Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44), can be dyed tovery good fastness properties. The process of dyeing on wool is herecarried out in a conventional manner from an acidic medium. Forinstance, acetic acid and/or ammonium sulfate or acetic acid andammonium sulfate or sodium acetate can be added to the dyebath to obtainthe desired pH. To obtain a dyeing of acceptable levelness, it isadvisable to add a customary leveling agent, for example a levelingagent based on a reaction product of cyanuric chloride with three timesthe molar amount of an aminobenzenesulfonic acid and/or of anaminonaphthalenesulfonic acid or on the basis of a reaction product offor example stearylamine with ethylene oxide. For instance, the dyemixture according to the invention is preferably subjected to theexhaust process initially from an acidic dyebath having a pH of about3.5 to 5.5 under pH control and the pH is then, toward the end of thedyeing time, shifted into the neutral and optionally weakly alkalinerange up to a pH of 8.5 to bring about, especially for very deepdyeings, the full reactive bond between the dyes of the dye mixturesaccording to the invention and the fiber. At the same time, the dyeportion not reactively bound is removed.

[0123] The procedure described herein also applies to the production ofdyeings on fiber materials composed of other natural polyamides or ofsynthetic polyamides and polyurethanes. In general, the material to bedyed is introduced into the bath at a temperature of about 40° C.,agitated therein for some time, the dyebath is then adjusted to thedesired weakly acidic, preferably weakly acetic acid, pH and the actualdyeing is carried out at a temperature between 60 and 98° C. However,the dyeings can also be carried out at the boil or in sealed dyeingapparatus at temperatures of up to 106° C. Since the water solubility ofthe dye mixtures according to the invention is very good, they can alsobe used with advantage in customary continuous dyeing processes. Thecolor strength of the dye mixtures according to the invention is veryhigh.

[0124] The dye mixtures according to the invention dye the materialsmentioned, preferably fiber materials, in navy to jet black shadeshaving good fastness properties.

[0125] The examples hereinbelow serve to illustrate the invention. Partsand percentages are by weight, unless otherwise stated. Parts by weightrelate to parts by volume as the kilogram relative to the liter. Thecompounds described in the examples in terms of a formula are indicatedin the form of the sodium salts, since they are generally prepared andisolated in the form of their salts, preferably lithium, sodium orpotassium salts, and used for dyeing in the form of their salts. Thestarting compounds described in the examples hereinbelow, especially thetable examples, can be used in the synthesis in the form of the freeacid or likewise in the form of their salts, preferably alkali metalsalts, such as sodium or potassium salts.

EXAMPLE 1

[0126] 85 parts of an electrolyte-containing dye powder containing thenavy disazo dye of the formula (IA)

[0127] in a 70% fraction and 15 parts of an electrolyte-containing dyepowder containing the orange-colored disazo dye of the formula (IIA) ina 75% fraction are mechanically mixed with each other.

[0128] The resulting dye mixture according to the invention provides jetblack dyeings and prints, on cotton for example, under the dyeingconditions customary for reactive dyes.

EXAMPLE 2

[0129] a) 281 parts of 4-(β-sulfatoethylsulfonyl)aniline are suspendedin 650 parts of ice-water and 180 parts of 30% hydrochloric acid anddiazotized by dropwise addition of 173 parts of 40% sodium nitritesolution. 319 parts of 1-amino-8-naphthol-3,6-disulfonic acid were addedand coupled in a first step at pH 1 to 1.3 at below 20° C. to form a redmonoazo dye conforming to the general formula (14). The stated pH rangeis set and maintained during the coupling reaction by addition of atotal of about 140 parts of sodium bicarbonate.

[0130] b) In a second, separate reaction vessel, 500 parts of4-amino-N-(3-((β-sulfatoethyl)-sulfonyl)-phenyl)-benzamide are suspendedin 2750 parts of ice-water, adjusted to pH 6.5-7 with about 90 parts ofsodium carbonate and admixed with 217 parts of 40% sodium nitritesolution. This suspension is added dropwise to a mixture of 780 parts ofice, 630 parts of ice-water and 450 parts of concentrated hydrochloricacid. After subsequent stirring at 5-10° C. for 2 hours, the excessnitrite is reduced with amidosulfonic acid and the resulting diazosuspension is pumped into the solution of the red monoazo dye of a).This reaction mixture is then admixed with 156.5 parts of the yellowmonoazo dye of the formula (17A), which was obtained by diazotization of90.5 parts of 4-(β-sulfatoethylsulfonyl)-2-sulfoaniline and subsequentcoupling onto 47 parts of 2,4-diaminobenzenesulfonic acid at pH 1.2-2.

[0131] The batch was then readjusted to pH 5-6 with sodium carbonate atbelow 25° C. and the 80:20 mixture of the dyes (IB) and (IIB) formedafter the coupling reaction has ended is isolated by spray drying.

[0132] Alternatively, the dye solution obtained can also be buffered atpH 5.5-6 by addition of a phosphate buffer and be adjusted by furtherdilution or concentration to provide a liquid brand of defined strength.

[0133] The resulting dye mixture according to the invention dyes cottonin black shades.

EXAMPLE 3

[0134] a) 281 parts of 4-(B-sulfatoethylsulfonyl)aniline are suspendedin 650 parts of ice-water and 180 parts of 30% hydrochloric acid anddiazotized by dropwise addition of 173 parts of 40% sodium nitritesolution. 271 parts of 1-amino-8-naphthol-3,6-disulfonic acid and 28parts of 2,4-diaminobenzenesulfonic acid were added and coupled in afirst step at pH 1 to 1.5 at below 20° C. to form a mixture of a red anda yellow monoazo dye conforming to the general formulae (14) and (17).The stated pH range is set and maintained during the coupling reactionby addition of a total of about 145 parts of sodium bicarbonate.

[0135] b) In a second, separate reaction vessel, 400 parts of4-amino-N-(3-((β-sulfatoethyl)-sulfonyl)-phenyl)-benzamide are suspendedin 2250 parts of ice-water, adjusted to pH 6.5-7 with about 72 parts ofsodium carbonate and admixed with 174 parts of 40% sodium nitritesolution. This suspension is added dropwise to a mixture of 625 parts ofice, 510 parts of ice-water and 360 parts of concentrated hydrochloricacid. After subsequent stirring at 5-10° C. for 2 hours, the excessnitrite is reduced with amidosulfonic acid and the resulting diazosuspension is pumped into the solution of the two monoazo dyes of a).

[0136] This is followed by setting pH 5-6 with sodium carbonate at below25° C. and the 87:13 mix of the dyes (IB) and (IIDH) formed after thecoupling reaction has ended is isolated by spray drying or evaporationunder reduced pressure.

[0137] The resulting dye mixture according to the invention dyes cottonin black shades.

EXAMPLE 4

[0138] 70 parts of an electrolyte-containing dye powder containing thenavy disazo dye of the formula (IA) in a 70% fraction and 30 parts of anelectrolyte-containing dye powder containing the brown disazo dye of theformula (IIIA)

[0139] in a 75% fraction are dissolved in 700 parts of water and theresulting dye solution is adjusted to pH 5.5-6.5. Evaporation of thisdye solution provides a dye mixture which provides navy to jet blackdyeings and prints on cotton under the dyeing conditions customary forreactive dyes.

EXAMPLES 5 to 545

[0140] The table examples hereinbelow describe further inventivemixtures of the dyes of the general formulae (I)-(III), each recited inthe form of the sodium salt. The mixing ratios are indicated in percentby weight. The dye mixtures provide jet black dyeings, on cotton forexample, by the dyeing methods customary for reactive dyes.

[0141] Dye mixtures according to example 1 Exam- Dye of gen. Ratio pleformula (I) Dye of gen. formula (II) (I):(II) 5 (IA)

85:15 6 (IA)

88:12 7 (IA)

80:20 8 (IA)

87:13 9 (IA)

88:12 10 (IA)

86:14 11 (IA)

75:25 12 (IA)

80:20 13 (IA)

78:22 14 (IA)

87:13 15 (IA)

86:14 16 (IA)

83:17 17 (IA)

82:18 18 (IA)

88:12 19 (IA)

86:14 20 (IA)

82:18 21 (IA)

88:12 22 (IA)

86:14 23 (IA)

87:13 24 (IA)

87:13 25 (IA)

85:15 26 (IA)

78:22 27 (IA)

77:23 28 (IA)

75:25 29 (IA)

74:26 30 (IA)

77:23 31 (IA)

80:20 32 (IA)

82:18 33 (IA)

87:13 34 (IA)

86:14 35 (IA)

83:17 36 (IA)

82:18 37 (IA)

84:16 38 (IA)

85:15 39 (IA)

83:17 40 (IA)

87:13 41 (IA)

82:18 42 (IA)

86:14 43 (IA)

82:18 44 (IA)

85:15 45 (IA)

87:13 46 (IA)

88:12 47 (IA)

80:20 48 (IA)

80:20 49 (IA)

85:15 50 (IA)

85:15 51 (IA)

82:18 52 (IA)

83:17 53 (IA)

84:16 54 (IA)

85:15 55 (IA)

85:15 56 (IA)

87:13 57 (IA)

88:12 58 (IA)

87:13 59 (IA)

85:15 60 (IA)

85:15 61 (IA)

80:20 62 (IA)

88:12 63 (IA)

85:15 64 (IA)

80:20 65 (IA)

80:20 66 (IA)

83:17 67 (IA)

80:20 68 (IA)

82:18 69 (IA)

83:17 70 (IA)

85:15 71 (IA)

80:20 72 (IA)

82:18 73 (IA)

85:15 74 (IA)

70:30 75 (IA)

75:25

EXAMPLES 76-147

[0142] Repetition of examples 1 and 5-75 using dye (IB) instead of dye(IA).

EXAMPLES 148-219

[0143] Repetition of examples 1 and 5-75 using dye (IC) instead of dye(IA):

EXAMPLES 220-291

[0144] Repetition of examples 1 and 5-75 using dye (ID) instead of dye(IA):

EXAMPLES 292-363

[0145] Repetition of examples 1 and 5-75 using dye (IE) instead of dye(IA):

[0146] Dye mixtures according to example 1 or 2 Dye of gen. RatioExample formula (I) Dye of gen. formula (II) (I):(II) 364 (IA)

80:20 365 (IB)

75:25 366 (IC)

78:22 367 (ID)

75:25 368 (IA)

84:16 369 (IC)

83:17 370 (ID)

85:15 371 (IA)

85:15 372 (IB)

82:18 373 (IC)

83:17 374 (ID)

82:18 375 (IA)

85:15 376 (IA)

85:15 377 (IB)

80:20 378

(IID) 85:15 379 (IF) (IIF) 85:15 380 (IF) (IIBD) 87:13 381 (IF)

75:25 382 (IF)

80:20 383 (IF)

80:20 384 (IF)

85:15 385 (IF)

87:13 386 (IF)

83:17 387 (IF)

77:23

EXAMPLES 388-397

[0147] Repetition of examples 378-387 using dye (IG) instead of dye(IF):

EXAMPLES 398-407

[0148] Repetition of examples 378-387 using dye (IH) instead of dye(IF):

EXAMPLES 408-417

[0149] Repetition of examples 378-387 using dye (IJ) instead of dye(IF):

[0150] Dye mixtures according to example 1 or 3 Dye of gen. Exampleformula (I) Dye of gen. Formula (II) Ratio (I):(II) 418 (IA)

87:13 419 (IB) (IIDH) 80:20 420 (IC)

86:14 421 (ID)

83:17 422 (IE)

80:20 423 (IF)

86:14 424 (IG)

84:16 425 (IH)

85:15 426 (IJ)

82:18

[0151] Dye mixtures according to example 4 Exam- Dye of gen. Ratio pleformula (I) Dye of gen. Formula (III) (I):(III) 427 (IA)

75:25 428 (IA)

80:20 429 (IA)

83:17 430 (IA)

82:18 431 (IA)

80:20 432 (IA)

80:20 433 (IA)

76:24 434 (IA)

80:20 435 (IA)

82:18 436 (IA)

75:25 437 (IA)

76:24 438 (IA)

77:23 439 (IA)

78:22 440 (IA)

75:25 441 (IA)

70:30 442 (IA)

82:18 443 (IA)

75:25 444 (IA)

80:20 445 (IA)

82:18 446 (IA)

80:20 447 (IA)

77:23 448 (IA)

75:25 449 (IA)

75:25

EXAMPLES 450-473

[0152] Repetition of examples 427-449 using dye (IB) instead of dye(IA).

EXAMPLES 474-497

[0153] Repetition of examples 4 and 427-449 using dye (IC) instead ofdye (IA).

EXAMPLES 498-521

[0154] Repetition of examples 4 and 427-449 using dye (ID) instead ofdye (IA).

EXAMPLES 522-545

[0155] Repetition of examples 4 and 427-449 using dye (IE) instead ofdye (IA).

USE EXAMPLE 1

[0156] 2 parts of a dye obtained according to example 1-4 are dissolvedin 999 parts of water and 5 parts of sodium carbonate, 0,7 part ofsodium hydroxide (in the form of a 32.5% aqueous solution) andoptionally 1 part of a wetting agent are added. The dyebath is enteredwith 100 g of a cotton fabric. The temperature of the dyebath is firstmaintained at 25° C. for 10 minutes, then raised over 30 minutes to thefinal temperature (40-60° C.) and maintained at that level for a further60-90 minutes. Thereafter, the dyed material is rinsed initially withtap water for 2 minutes and then with ion-free water for 5 minutes. Thedyed material is neutralized at 40° C. in 1000 parts of an aqueoussolution containing 1 part of 50% acetic acid for 10 minutes. It issubsequently rinsed with ion-free water at 70° C. and thereafter soakedoff at the boil with a detergent for 15 minutes, rinsed once more anddried. This gives a strong navy to gray dyeing having very good fastnessproperties.

USE EXAMPLE 2

[0157] 4 parts of a dye obtained according to example 1-4 and 5 parts ofsodium chloride are dissolved in 999 parts of water, 7 parts of sodiumcarbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueoussolution) and optionally 1 part of a wetting agent are added. Thisdyebath is entered with 100 g of a cotton fabric. The rest of theprocessing is as indicated in use example 1. This gives a strong navy toblack dyeing having very good fastness properties.

USE EXAMPLE 3

[0158] 8 parts of a dye obtained according to example 1-4 and 10 partsof sodium chloride are dissolved in 997 parts of water, 10 parts ofsodium carbonate, 1.3 parts of sodium hydroxide (in the form of a 32.5%aqueous solution) and optionally 1 part of a wetting agent are added.This dyebath is entered with 100 g of a cotton fabric. The rest of theprocessing is as indicated in use example 1. This gives a jet blackdyeing having very good fastness properties.

We claim:
 1. Reactive dye mixtures comprising one or more dyes of thehereinbelow indicated and defined general formula (I)

and one or more dyes of the hereinbelow indicated and defined generalformula (II)

or one or more dyes of the hereinbelow indicated and defined generalformula (III)

where: D¹ and D² are each a group of the general formula (1)

where R¹ is hydrogen, (C₁-C₄)-alkyl, aryl or a substituted aryl radical;R² and R³ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,hydroxyl, sulfo, carboxyl, amido or halogen; and A is a phenylene groupof the general formula (2)

 where R⁴ and R⁵ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or anaphthylene group of the general formula (3)

 where R⁶ and R⁷ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or apolymethylene group of the general formula (4) —(CR⁸R⁹)_(k)—  (4)  wherek is an integer greater than 1 and R⁸ and R⁹ are independently hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, cyano, amido, halogen or aryl;and X¹ is hydrogen or a group of the formula —SO₂-Z; or are each aphenyl group of the general formula (5)

where R¹⁰ and R¹¹ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X² hasone of the meanings of X¹; or are each a naphthyl group of the generalformula (6)

where R¹² and R¹³ are independently hydrogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X³ hasone of the meanings of X¹; Z is —CH═CH₂, —CH₂CH₂Z¹ or hydroxyl, where Z¹is hydroxyl or an alkali-eliminable group; and M is hydrogen, an alkalimetal or one equivalent of an alkaline earth metal; D³ and D⁴independently have one of the meanings of D¹ or D² or each a group ofthe general formula (7) or (8)

 where R²² and R²³ independently have one of the meanings of R² and R³;R²¹ is hydrogen, (C₁-C₄)-alkyl, unsubstituted or (C₁-C₄)-alkyl-,(C₁-C₄)-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; andZ²¹ is a heterocyclic reactive radical, and Z is as defined above; R²⁴,R²⁵ and R²⁶ are each (C₁-C₄)-alkyl or (C₁-C₄)-hydroxyalkyl; B⁻ is theequivalent of an anion, such as hydrogensulfate, sulfate, fluoride,chloride, bromide, dihydrogenphosphate, hydrogenphosphate, phosphate,hydroxide or acetate; R³¹, R³², R³³ are independently hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, carboxyl, halogen,(C₁-C₄)-alkylcarbonylamino, benzoylamino, ureido; Z³¹ has one of themeanings of Z²¹; a, b, c are independently 0 or 1; f, r areindependently 0, 1 or 2; and t is 0, 1, 2 or 3; at least one of D¹ andD² is a group of the general formula (1); when A is a group of thegeneral formula (4), R¹ is aryl or substituted aryl; and the reactivedye of the general formula (I) contains at least one —SO₂-Z group. 2.Reactive dye mixtures as claimed in claim 1, wherein the heterocyclicreactive radical Z²¹ is a group of the general formula (9) or (10) or(11)

where V is fluorine or chlorine; U¹ and U² are independently fluorine,chlorine or hydrogen; and Q¹ and Q² are independently chlorine,fluorine, cyanamido, hydroxyl, (C₁-C₆)-alkoxy, phenoxy, sulfophenoxy,mercapto, (C₁-C₆)-alkylmercapto, pyridino, carboxypyridino,carbamoylpyrimidino or a group of the general formula (12) or (13)

 where R²′, is hydrogen or (C₁-C₆)-alkyl, sulfo-(C₁-C₆)-alkyl, or phenylwhich is unsubstituted or substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,sulfo, halogen, carboxyl, acetamido or ureido; R³′ and R⁴′ independentlyhave one of the meanings of R²′ or are each a group of the generalformula (8), or combine to form a cyclic ring system of the formula—(CH₂)_(j)—, where j is 4 or 5, or alternatively —(CH₂)₂-E-(CH₂)₂—,where E is oxygen, sulfur, sulfo, —NR⁵′—, where R⁵′═(C₁-C₆)-alkyl; W isphenylene which is unsubstituted or substituted by 1 or 2 substituents,such as (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, carboxyl, sulfo, chlorine,bromine, or is (C₁-C₄)-alkylene-arylene or (C₂-C₆)-alkylene, which canbe interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamido,or is phenylene-CONH-phenylene, which is unsubstituted or substituted by(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureidoor halogen, or is naphthylene, which is unsubstituted or substituted byone or two sulfo groups; and the substituents R¹ to R⁵, R⁸ to R¹¹, R²¹and R³¹ are each hydrogen, R⁶, R⁷, R¹², R¹³, R²² and R²³ are eachhydrogen or sulfo, R²⁴, R²⁵ and R²⁶ are each methyl, R³² is hydrogen ormethyl and R³³ is hydrogen, methyl or methoxy.
 3. Reactive dye mixturesas claimed in at least one of claims 1 and 2, wherein Z is vinyl,β-chloroethyl or β-sulfatoethyl.
 4. Reactive dye mixtures as claimed inat least one of claims 1 to 3, wherein D³ or D⁴ in the general formula(II) is 3-(β-sulfatoethylsulfonyl)-phenyl,4-(β-sulfatoethylsulfonyl)-phenyl,2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl,2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl, 3- or4-vinylsulfonyl-phenyl,4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl,4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl,3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl,3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl,1-sulfo-4-(2,4-difluoro-pyrimidin-6-yl)-amino-2-phenyl, or1-sulfo-4-(4,6-difluoro-pyrimidin-2-yl)-amino-2-phenyl.
 5. Reactive dyemixtures as claimed in at least one of claims 1 to 4, wherein Z³¹ in thegeneral formula (III) is 2,4-dichloro-1,3,5-triazin-6-yl,2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenyl-amino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenyl-amino)-1,3,5-trazin-6-yl,2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-morpholino-1,3,5-triazin-6-yl,2-fluoro-4-(2-sulfophenyl-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-trimethylammonio-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-trimethylammoniophenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl,2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl,5-chloro-2,4-difluoro-pyrimidin-6-yl,5-chloro-4,6-difluoro-pyrimidin-2-yl or2,3-dichloroquinoxaline-6-carbonyl.
 6. Reactive dye mixtures as claimedin at least one of claims 1 to 5, comprising at least one dye of thegeneral Formula (Ia)

and at least one dye of the general Formula (IIa)

or at least one dye of the general formula (IIIa)

where M, A, R¹, Z, R³¹, R³³, Z³¹ and t are each as defined in claim 1and R¹⁰³, R¹¹³, R¹⁰⁴ and R¹¹⁴ in the general formula (IIa) areindependently hydrogen, methyl, methoxy or sulfo.
 7. A reactive dyemixture as claimed in claim 6, wherein A in the formula (Ia) isphenylene, Z in the formulae (Ia) and (IIa) is vinyl or β-sulfatoethyland t in the formula (IIIa) is 1 or 2 and Z³¹ in the formula (IIIa) isas defined in claim
 1. 8. Reactive dye mixtures as claimed in one ormore of claims 1 to 7, comprising one or more dyes of the formula (I) ina fraction of 30 to 95% by weight and one or more dyes of the formula(II) or (III) in a fraction of 5 to 70% by weight.
 9. Reactive dyemixtures as claimed in claim 1, comprising one or more monoazo dyes ofthe formula (14) and/or one or more monoazo dyes of the formula (15)each at 0.5 to 6% by weight

where D² and M are each as defined in claim
 1. 10. A process forproducing dye mixtures as claimed in one or more of claims 1 to 8, whichcomprises the individual dyes of the formulae (I) and (II) or (III) and,if used, (14) and (15) being mixed with each other in the requiredproportions either mechanically in solid form or in the form of aqueoussolutions.
 11. A process for producing dye mixtures as claimed in one ormore of claims 1 to 8 for the case where D¹ and D⁴ in the generalformulae (I) and (II) are the same, which comprises diazotizing an amineof the general formula (16) D¹—NH₂  (16), where D¹ is as defined inclaim 1, in a conventional manner and then reacting the resultingdiazonium compound with an aqueous solution or suspension of a mixturehaving a defined ratio of a monoazo dye conforming to the generalformula (14) and a monoazo dye conforming to the general formula (17)

where D², D³ and M are each as defined in claim
 1. 12. A process forproducing dye mixtures as claimed in one of claims 1 to 8 for the casewhere the groups D² and D³ and also D¹ and D⁴ in the general formulae(I) and (II) are the same (D²=D³ and D¹=D⁴), which comprises diazotizingan amine of the general formula (18) D²—NH₂  (18) where D² is as definedin claim 1, in a conventional manner and coupling the resultingdiazonium compound onto a mixture of the coupling components and thendiazotizing an amine of the general formula (16) where D¹ is as definedin claim 1 in a conventional manner and coupling the resulting diazoniumcompound with the mixture of the monoazo dyes of the general formulae(14) and (17) which is obtained in the first step.
 13. The use ofreactive dye mixtures of one or more of claims 1 to 9 for dyeinghydroxyl- and/or carboxamido-containing fiber material.